Polyol esters of metathesized fatty acids and uses thereof

ABSTRACT

Polyol esters of metathesized fatty acids are generally disclosed herein. Methods of using such compounds, for example, as cleaning agents, solvents, and coalescents for paints and coatings, are also disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation application of U.S. patentapplication Ser. No. 15/149,177, filed May 8, 2016, which is acontinuation-in-part application of U.S. patent application Ser. No.15/075,734, filed Mar. 21, 2016, which claims the benefit of priority ofU.S. Provisional Application Nos.: 62/137,685, filed Mar. 24, 2015; and62/236,034, filed Oct. 1, 2015. All of the foregoing applications arehereby incorporated by reference as though set forth herein in theirentirety.

TECHNICAL FIELD

Polyol esters of metathesized fatty acids are generally disclosedherein. Methods of using such compounds, for example, as cleaningagents, solvents, and coalescents for paints and coatings, are alsodisclosed.

BACKGROUND

Natural oils, such as seed oils, and their derivatives can provideuseful starting materials for making a variety of chemical compounds.Because such compounds contain a certain degree of inherentfunctionality that is otherwise absent from petroleum-sourced materials,it can often be more desirable, if not cheaper, to use natural oils ortheir derivatives as a starting point for making certain compounds.Additionally, natural oils and their derivatives are generally sourcedfrom renewable feedstocks. Thus, by using such starting materials, onecan enjoy the concomitant advantage of developing useful chemicalproducts without consuming limited supplies of petroleum. Further,refining natural oils can be less intensive in terms of the severity ofthe conditions required to carry out the refining process.

Natural oils can be refined in a variety of ways. For example, processesthat rely on microorganisms can be used, such as fermentation. Chemicalprocesses can also be used. For example, when the natural oils containat least one carbon-carbon double bond, olefin metathesis can provide auseful means of refining a natural oil and making useful chemicals fromthe compounds in the feedstock.

Metathesis is a catalytic reaction that involves the interchange ofalkylidene units among compounds containing one or more double bonds(e.g., olefinic compounds) via the cleavage and formation ofcarbon-carbon double bonds. Metathesis may occur between two likemolecules (often referred to as “self-metathesis”) or it may occurbetween two different molecules (often referred to as“cross-metathesis”). Self-metathesis may be represented schematically asshown below in Equation (A):R^(a)—CH═CH—R^(b)+R^(a)—CH═CH—R^(b)↔R^(a)—CH═CH—R^(a)+R^(b)—CH═CH—R^(b),  (A)wherein R^(a) and R^(b) are organic groups.

Cross-metathesis may be represented schematically as shown below inEquation (B):R^(a)—CH═CH—R^(b)+R^(c)—CH═CH—R^(d)↔R^(a)—CH═CH—R^(c)+R^(a)—CH═CH—R^(d)+R^(b)—CH═CH—R^(c)+R^(b)—CH═CH—R^(d),  (B)wherein R^(a), R^(b), R^(c), and R^(d) are organic groups.Self-metathesis will also generally occur concurrently withcross-metathesis.

In recent years, there has been an increased demand for environmentallyfriendly techniques for manufacturing materials typically derived frompetroleum sources, which can be made by processes that involve olefinmetathesis. This has led to studies of the feasibility of manufacturingbiofuels, waxes, plastics, and the like, using natural oil feedstocks,such as vegetable and/or seed-based oils.

Natural oil feedstocks of interest include, but are not limited to, oilssuch as natural oils (e.g., vegetable oils, fish oils, algae oils, andanimal fats), and derivatives of natural oils, such as free fatty acidsand fatty acid alkyl (e.g., methyl) esters. These natural oil feedstocksmay be converted into industrially useful chemicals (e.g., waxes,plastics, cosmetics, biofuels, etc.) by any number of differentmetathesis reactions. Significant reaction classes include, asnon-limiting examples, self-metathesis, cross-metathesis with olefins,and ring-opening metathesis reactions. Non-limiting examples of usefulmetathesis catalysts are described in further detail below.

Refining processes for natural oils (e.g., employing metathesis) canlead to compounds having chain lengths closer to those generally desiredfor chemical intermediates of specialty chemicals (e.g., about 9 to 15carbon atoms). By using these compounds as starting materials, it ispossible to create a variety of novel chemical compounds that may beused for a variety of useful purposes. Further, because these compoundscontain somewhat different chemical functionality than similarmolecular-weight compounds derived in other ways, metathesis-derivedvariants may have beneficial properties that could not have beenappreciated otherwise.

Meanwhile, the use of certain industrial solvents has curtailed inrecent years due, in part, to concerns over their impact on theenvironment and their effects on general health and safety. This isespecially true of solvents known to have a high volatile organiccontent (VOC), as such compounds may contribute to greenhouse gasproduction and ozone depletion. In some instances, traditional high VOCsolvents can also be carcinogenic, teratogenic, toxic, and/or mutagenic.Therefore, a number of common solvents have come under increasedregulatory scrutiny and therefore suffer from decreased use. Suchsolvents include aromatics (e.g., benzene, toluene, xylenes, and thelike), ketones (e.g., methyl ethyl ketone, methyl isobutyl ketone, andthe like), halogenated organics (e.g., dichloromethane,perchloroethylene, and the like), glycol ethers, and alcohols (e.g.,methanol, isopropanol, ethylene glycol, and the like).

Certain derivatives of renewable feedstocks can provide more suitablealternatives to high VOC solvents. For example, fatty acid alkyl esters(e.g., from the transesterification of vegetable oils, animal fats, orother lipids) can provide environmentally friendly alternatives totraditional oxygenated solvents. Methyl soyate, for example, has a lowVOC value, a high flash point, a low toxicity, and a highbiodegradability. Terpene oils from citrus and pine (d-limonene andpinene, respectively) may also serve as suitable alternatives to certaintraditional organic solvents.

Such renewable solvents are not without their problems, however. Forexample, d-limonene and dipentene (a racemate of d-limonene) are bothacute and chronic aquatic toxins, and also have an irritating andsensitizing effect on the skin. Further, d-limonene is highlyinflammable (e.g., more so than petroleum distillates) and can besubject to fluctuations in supply and price. Fatty acid alkyl esters canovercome some of these deficiencies of terpene oils, but can alsoexhibit poor solvency relative to certain incumbents.

Thus, there is a continuing need to develop solvent compounds andcompositions that are renewably sourced, exhibit high solvency, and havea desirable health and safety profile (e.g., in terms of toxicity andVOCs).

SUMMARY

In a first aspect, the disclosure provides compounds derived from themetathesis of a natural oil that provide low VOCs and that functioneffectively in many solvent-related applications.

In a second aspect, the disclosure provides a compound of formula (I):

wherein: R¹ is —H, —CH₂—CH₃, —CH₂—CH═CH₂, or —CH₂—CH═CH—CH₂—CH₃, R² is—(C₂₋₁₀ alkylene)-(OH)q; and q is 1, 2, or 3.

In a third aspect, the disclosure provides cleaning compositions thatinclude one or more compounds of the second or third aspects. In someembodiments thereof, the cleaning composition includes a carrier, and,optionally, a surfactant.

In a fourth aspect, the disclosure provides petroleum compositions thatinclude one or more compounds of the second or third aspects and apetroleum fluid.

In a fifth aspect, the disclosure provides paint or coating compositionsthat include water, a film-forming polymer, and one or more compounds ofthe second or third aspects.

In a sixth aspect, the disclosure provides methods for painting orcoating a surface, comprising disposing a composition of the sixthaspect on the surface.

Further aspects and embodiments are provided in the foregoing drawings,detailed description and claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The following drawings are provided for purposes of illustrating variousembodiments of the compositions and methods disclosed herein. Thedrawings are provided for illustrative purposes only, and are notintended to describe any preferred compositions or preferred methods, orto serve as a source of any limitations on the scope of the claimedinventions.

FIG. 1 shows a non-limiting example of a compound made according tocertain embodiments disclosed herein, wherein: R¹ is —H, —CH₂—CH₃,—CH₂—CH═CH₂, or —CH₂—CH═CH—CH₂—CH₃, R² is —(C₂₋₁₀alkylene)-(OH)q, and qis 1, 2, or 3.

DETAILED DESCRIPTION

The following description recites various aspects and embodiments of theinventions disclosed herein. No particular embodiment is intended todefine the scope of the invention. Rather, the embodiments providenon-limiting examples of various compositions, and methods that areincluded within the scope of the claimed inventions. The description isto be read from the perspective of one of ordinary skill in the art.Therefore, information that is well known to the ordinarily skilledartisan is not necessarily included.

Definitions

The following terms and phrases have the meanings indicated below,unless otherwise provided herein. This disclosure may employ other termsand phrases not expressly defined herein. Such other terms and phrasesshall have the meanings that they would possess within the context ofthis disclosure to those of ordinary skill in the art. In someinstances, a term or phrase may be defined in the singular or plural. Insuch instances, it is understood that any term in the singular mayinclude its plural counterpart and vice versa, unless expresslyindicated to the contrary.

As used herein, the singular forms “a,” “an,” and “the” include pluralreferents unless the context clearly dictates otherwise. For example,reference to “a substituent” encompasses a single substituent as well astwo or more substituents, and the like.

As used herein, “for example,” “for instance,” “such as,” or “including”are meant to introduce examples that further clarify more generalsubject matter. Unless otherwise expressly indicated, such examples areprovided only as an aid for understanding embodiments illustrated in thepresent disclosure, and are not meant to be limiting in any fashion. Nordo these phrases indicate any kind of preference for the disclosedembodiment.

As used herein, “natural oil,” “natural feedstock,” or “natural oilfeedstock” refer to oils derived from plants or animal sources. Theseterms include natural oil derivatives, unless otherwise indicated. Theterms also include modified plant or animal sources (e.g., geneticallymodified plant or animal sources), unless indicated otherwise. Examplesof natural oils include, but are not limited to, vegetable oils, algaeoils, fish oils, animal fats, tall oils, derivatives of these oils,combinations of any of these oils, and the like. Representativenon-limiting examples of vegetable oils include rapeseed oil (canolaoil), coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanutoil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil,palm kernel oil, tung oil, jatropha oil, mustard seed oil, pennycressoil, camelina oil, hempseed oil, and castor oil. Representativenon-limiting examples of animal fats include lard, tallow, poultry fat,yellow grease, and fish oil. Tall oils are by-products of wood pulpmanufacture. In some embodiments, the natural oil or natural oilfeedstock comprises one or more unsaturated glycerides (e.g.,unsaturated triglycerides). In some such embodiments, the natural oilfeedstock comprises at least 50% by weight, or at least 60% by weight,or at least 70% by weight, or at least 80% by weight, or at least 90% byweight, or at least 95% by weight, or at least 97% by weight, or atleast 99% by weight of one or more unsaturated triglycerides, based onthe total weight of the natural oil feedstock.

As used herein, “natural oil derivatives” refers to the compounds ormixtures of compounds derived from a natural oil using any one orcombination of methods known in the art. Such methods include but arenot limited to saponification, fat splitting, transesterification,esterification, hydrogenation (partial, selective, or full),isomerization, oxidation, and reduction. Representative non-limitingexamples of natural oil derivatives include gums, phospholipids,soapstock, acidulated soapstock, distillate or distillate sludge, fattyacids and fatty acid alkyl ester (e.g. non-limiting examples such as2-ethylhexyl ester), hydroxy substituted variations thereof of thenatural oil. For example, the natural oil derivative may be a fatty acidmethyl ester (“FAME”) derived from the glyceride of the natural oil. Insome embodiments, a feedstock includes canola or soybean oil, as anon-limiting example, refined, bleached, and deodorized soybean oil(i.e., RBD soybean oil). Soybean oil typically comprises about 95%weight or greater (e.g., 99% weight or greater) triglycerides of fattyacids. Major fatty acids in the polyol esters of soybean oil includesaturated fatty acids, as a non-limiting example, palmitic acid(hexadecanoic acid) and stearic acid (octadecanoic acid), andunsaturated fatty acids, as a non-limiting example, oleic acid(9-octadecenoic acid), linoleic acid (9, 12-octadecadienoic acid), andlinolenic acid (9,12,15-octadecatrienoic acid).

As used herein, “metathesis catalyst” includes any catalyst or catalystsystem that catalyzes an olefin metathesis reaction.

As used herein, “metathesize” or “metathesizing” refer to the reactingof a feedstock in the presence of a metathesis catalyst to form a“metathesized product” comprising new olefinic compounds, i.e.,“metathesized” compounds. Metathesizing is not limited to any particulartype of olefin metathesis, and may refer to cross-metathesis (i.e.,co-metathesis), self-metathesis, ring-opening metathesis, ring-openingmetathesis polymerizations (“ROMP”), ring-closing metathesis (“RCM”),and acyclic diene metathesis (“ADMET”). In some embodiments,metathesizing refers to reacting two triglycerides present in a naturalfeedstock (self-metathesis) in the presence of a metathesis catalyst,wherein each triglyceride has an unsaturated carbon-carbon double bond,thereby forming a new mixture of olefins and esters which may include atriglyceride dimer. Such triglyceride dimers may have more than oneolefinic bond, thus higher oligomers also may form. Additionally, insome other embodiments, metathesizing may refer to reacting an olefin,such as ethylene, and a triglyceride in a natural feedstock having atleast one unsaturated carbon-carbon double bond, thereby forming newolefinic molecules as well as new ester molecules (cross-metathesis).

As used herein, “olefin” or “olefins” refer to compounds having at leastone unsaturated carbon-carbon double bond. In certain embodiments, theterm “olefins” refers to a group of unsaturated carbon-carbon doublebond compounds with different carbon lengths. Unless noted otherwise,the terms “olefin” or “olefins” encompasses “polyunsaturated olefins” or“poly-olefins,” which have more than one carbon-carbon double bond. Asused herein, the term “monounsaturated olefins” or “mono-olefins” refersto compounds having only one carbon-carbon double bond. A compoundhaving a terminal carbon-carbon double bond can be referred to as a“terminal olefin,” while an olefin having a non-terminal carbon-carbondouble bond can be referred to as an “internal olefin.”

As used herein, the term “low-molecular-weight olefin” may refer to anyone or combination of unsaturated straight, branched, or cyclichydrocarbons in the C₂₋₁₄ range. Low-molecular-weight olefins include“alpha-olefins” or “terminal olefins,” wherein the unsaturatedcarbon-carbon bond is present at one end of the compound.Low-molecular-weight olefins may also include dienes or trienes.Low-molecular-weight olefins may also include internal olefins or“low-molecular-weight internal olefins.” In certain embodiments, thelow-molecular-weight internal olefin is in the 04-14 range. Examples oflow-molecular-weight olefins in the 02-6 range include, but are notlimited to: ethylene, propylene, 1-butene, 2-butene, isobutene,1-pentene, 2-pentene, 3-pentene, 2-methyl-1-butene, 2-methyl-2-butene,3-methyl-1-butene, cyclopentene, 1,4-pentadiene, 1-hexene, 2-hexene,3-hexene, 4-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 2-methyl-2-pentene, 3-methyl-2-pentene,4-methyl-2-pentene, 2-methyl-3-pentene, and cyclohexene. Non-limitingexamples of low-molecular-weight olefins in the 07-9 range include1,4-heptadiene, 1-heptene, 3,6-nonadiene, 3-nonene, 1,4,7-octatriene.Other possible low-molecular-weight olefins include styrene and vinylcyclohexane. In certain embodiments, it is preferable to use a mixtureof olefins, the mixture comprising linear and branchedlow-molecular-weight olefins in the C₄₋₁₀ range. In one embodiment, itmay be preferable to use a mixture of linear and branched C₄ olefins(i.e., combinations of: 1-butene, 2-butene, and/or isobutene). In otherembodiments, a higher range of C₁₁₋₁₄ may be used.

In some instances, the olefin can be an “alkene,” which refers to astraight- or branched-chain non-aromatic hydrocarbon having 2 to 30carbon atoms and one or more carbon-carbon double bonds, which may beoptionally substituted, as herein further described, with multipledegrees of substitution being allowed. A “monounsaturated alkene” refersto an alkene having one carbon-carbon double bond, while a“polyunsaturated alkene” refers to an alkene having two or morecarbon-carbon double bonds. A “lower alkene,” as used herein, refers toan alkene having from 2 to 10 carbon atoms.

As used herein, “alpha-olefin” refers to an olefin (as defined above)that has a terminal carbon-carbon double bond. In some embodiments, thealpha-olefin is a terminal alkene, which is an alkene (as defined above)having a terminal carbon-carbon double bond. Additional carbon-carbondouble bonds can be present.

As used herein, “ester” or “esters” refer to compounds having thegeneral formula: R—COO—R′, wherein R and R′ denote any organic group(such as alkyl, aryl, or silyl groups) including those bearingheteroatom-containing substituent groups. In certain embodiments, R andR′ denote alkyl, alkenyl, aryl, or alcohol groups. In certainembodiments, the term “esters” may refer to a group of compounds withthe general formula described above, wherein the compounds havedifferent carbon lengths. In certain embodiments, the esters may beesters of glycerol, which is a trihydric alcohol. The term “glyceride”can refer to esters where one, two, or three of the —OH groups of theglycerol have been esterified.

It is noted that an olefin may also comprise an ester, and an ester mayalso comprise an olefin, if the R or R′ group in the general formulaR—COO—R′ contains an unsaturated carbon-carbon double bond. Suchcompounds can be referred to as “unsaturated esters” or “olefin esters.”Further, a “terminal olefin ester” may refer to an ester compound whereR has an olefin positioned at the end of the chain. An “internal olefinester” may refer to an ester compound where R has an olefin positionedat an internal location on the chain. Additionally, the term “terminalolefin” may refer to an ester or an acid thereof where R′ denoteshydrogen or any organic compound (such as an alkyl, aryl, or silylgroup) and R has an olefin positioned at the end of the chain, and theterm “internal olefin” may refer to an ester or an acid thereof where R′denotes hydrogen or any organic compound (such as an alkyl, aryl, orsilyl group) and R has an olefin positioned at an internal location onthe chain.

As used herein, “mix” or “mixed” or “mixture” refers broadly to anycombining of two or more compositions. The two or more compositions neednot have the same physical state; thus, solids can be “mixed” withliquids, e.g., to form a slurry, suspension, or solution. Further, theseterms do not require any degree of homogeneity or uniformity ofcomposition. This, such “mixtures” can be homogeneous or heterogeneous,or can be uniform or non-uniform. Further, the terms do not require theuse of any particular equipment to carry out the mixing, such as anindustrial mixer.

As used herein, “optionally” means that the subsequently describedevent(s) may or may not occur. In some embodiments, the optional eventdoes not occur. In some other embodiments, the optional event does occurone or more times.

As used herein, “comprise” or “comprises” or “comprising” or “comprisedof” refer to groups that are open, meaning that the group can includeadditional members in addition to those expressly recited. For example,the phrase, “comprises A” means that A must be present, but that othermembers can be present too. The terms “include,” “have,” and “composedof” and their grammatical variants have the same meaning. In contrast,“consist of” or “consists of” or “consisting of” refer to groups thatare closed. For example, the phrase “consists of A” means that A andonly A is present.

As used herein, “or” is to be given its broadest reasonableinterpretation, and is not to be limited to an either/or construction.Thus, the phrase “comprising A or B” means that A can be present and notB, or that B is present and not A, or that A and B are both present.Further, if A, for example, defines a class that can have multiplemembers, e.g., A₁ and A₂, then one or more members of the class can bepresent concurrently.

As used herein, the various functional groups represented will beunderstood to have a point of attachment at the functional group havingthe hyphen or dash (-) or an asterisk (*). In other words, in the caseof —CH₂CH₂CH₃, it will be understood that the point of attachment is theCH₂ group at the far left. If a group is recited without an asterisk ora dash, then the attachment point is indicated by the plain and ordinarymeaning of the recited group.

In some instances herein, organic compounds are described using the“line structure” methodology, where chemical bonds are indicated by aline, where the carbon atoms are not expressly labeled, and where thehydrogen atoms covalently bound to carbon (or the C—H bonds) are notshown at all. For example, by that convention, the formula

represents n-propane. In some instances herein, a squiggly bond is usedto show the compound can have any one of two or more isomers. Forexample, the structure

can refer to (E)-2-butene or (Z)-2-butene.

As used herein, multi-atom bivalent species are to be read from left toright. For example, if the specification or claims recite A-D-E and D isdefined as —OC(O)—, the resulting group with D replaced is: A-OC(O)-Eand not A-C(O)O-E.

Other terms are defined in other portions of this description, eventhough not included in this subsection.

Polyol Esters of Unsaturated Fatty Acids

In certain aspects, the disclosure provides polyol esters of unsaturatedfatty acids. In some embodiments, the polyol esters of unsaturated fattyacids are compounds of formula (I):

wherein: R¹ is —H, —CH₂—CH₃, —CH₂—CH═CH₂, or —CH₂—CH═CH—CH₂—CH₃; R² is—(C₂₋₁₀ alkylene)-(OH)q; and q is 1, 2, or 3.

In some embodiments, R¹ is —H. In some other embodiments, R¹ is—CH₂—CH₃, —CH₂—CH═CH₂, or —CH₂—CH═CH—CH₂—CH₃. In some such embodiments,R¹ is —CH₂—CH₃. In some such embodiments, R¹ is —CH₂—CH═CH₂. In somesuch embodiments, R¹ is —CH₂—CH═CH—CH₂—CH₃.

In some embodiments of any of the foregoing embodiments, q is 1 or 2. Insome such embodiments, q is 1. In some such embodiments, q is 2.

In some embodiments of any of the foregoing embodiments, R² is —(C₂₋₁₀alkylene)-OH. In some such embodiments, R² is —(CH₂)₂—OH, —(CH₂)₃—OH,—(CH₂)₄—OH, —(CH₂)₅—OH, —(CH₂)₆—OH, —CH(OH)—CH₃, —CH₂—CH(OH)—CH₃,—CH(CH₃)—CH₂—OH, —CH₂—CH(CH₃)—CH₂—OH, or —CH₂—C(CH₃)₂—CH(OH)—CH(CH₃)₂.In some further such embodiments, R² is —(CH₂)₂—OH. In some other suchembodiments, R² is —(CH₂)₃—OH. In some other such embodiments, R² is—(CH₂)₄—OH. In some other such embodiments, R² is —CH(OH)—CH₃. In someother such embodiments, R² is —CH₂—CH(OH)—CH₃. In some other suchembodiments, R² is —CH(CH₃)—CH₂—OH. In some other such embodiments, R²is —CH₂—CH(CH₃)—CH₂—OH. In some other such embodiments, R² is—CH₂—C(CH₃)₂—CH(OH)—CH(CH₃)₂.

Cleaning Compositions

In certain aspects, the disclosure provides compositions that include apolyol ester of an unsaturated fatty acid (according to any of the aboveembodiments), e.g., as a cleaning agent.

In some embodiments, the composition consists of or consists essentiallyof the polyol ester of an unsaturated fatty acid. In some otherembodiments, however, the composition includes water. In some suchembodiments, the composition further includes a surfactant, such as anon-ionic surfactant, an anionic surfactants, a cationic surfactant, orcombinations thereof. In some embodiments, the composition is anemulsion, such as a micro-emulsion. In some such embodiments, theemulsion is an oil-in-water emulsion. In some other embodiments, theemulsion is a water-in-oil emulsion.

The cleaning agents disclosed above can be used in various cleaningapplications, including, but not limited to, degreasing, such asindustrial degreasing, cleaning textiles or other woven fibers, such asin laundry-related applications (e.g., pre-treatment or detergent),cleaning food or food residues, or cleaning oilfield-related equipment,such as cleaning materials containing paraffins, asphaltenes, and thelike.

Petroleum Compositions

In certain aspects, the disclosure provides petroleum compositions thatinclude a petroleum fluid and a polyol ester of an unsaturated fattyacid (according to any of the above embodiments), e.g., as an agent forimproving the pour point by dissolving paraffins and/or asphaltenes. Insome embodiments, the petroleum fluid is crude oil.

Coating or Paint Compositions Including a Coalescing Aid

In certain aspects, the disclosure provides compositions that include anaqueous carrier, a film-forming polymer, and a polyol ester of anunsaturated fatty acid (according to any of the above embodiments),e.g., as a coalescing aid.

The compositions comprise an aqueous carrier and a film-forming polymer.Any suitable aqueous carrier can be used. In general, water is thepredominant component of the aqueous carrier, although amounts ofadditional ingredients can be dissolved in the water. Such additionalingredients include, but are not limited to, surfactants, thickeners,rheology modifiers, pigments or other colorants, defoamers, co-solvents,and the like. Suitable co-solvents include solvents that are misciblewith water. In some embodiments, one or more of these additionalingredients may, in addition to being dissolved in the aqueous medium,be suspended in the aqueous medium (e.g., as part of an emulsion). Insome embodiments, the aqueous medium comprises at least 70% by weight,or at least 80% by weight, or at least 90% by weight, or at least 95% byweight, or at least 97% by weight, water.

In some embodiments, it may be desirable to adjust the pH of the aqueousmedium, depending, for example, on whether one or more components in thecomposition may perform better for certain end uses. In someembodiments, the aqueous medium is approximately neutral, meaning thatit has a pH of 6 to 8. In some other embodiments, the aqueous medium isan acidic medium, such as, for example, a medium having a pH less than7. In some such embodiments, the pH is in the range of 3 to 7 (but notincluding 7), or 4 to 6. In some other embodiments, the aqueous mediumis alkaline, such as, for example, a medium having a pH greater than 7.In some such embodiments, the pH is in the range of 7 (but not including7) to 11, or 8 to 10.

The composition also includes one or more film-forming polymers. In someembodiments, the film-forming polymer is a water-dispersible polymer. Insome such embodiments, the film-forming polymer exists in thecomposition as a separate phase, which, for example, is dispersed in theaqueous medium. In some embodiments, the dispersed polymer can form aplurality of droplets that are dispersed in the aqueous medium. In somesuch embodiments, the droplets are dispersed in a manner so as to forman emulsion. In some instances, however, the composition may tend tophase separate into distinct layers, such as instances where thecomposition is left to sit for some length of time. Such phase-separated(or partially phase-separated) compositions are also within the scope ofthe disclosed compositions. In some embodiments, a small amount of thefilm-forming polymer may dissolve in the aqueous medium, although, inmost embodiments, a predominant amount (e.g., at least 80% by weight, orat least 90% by weight, or at least 95% by weight, or at least 97% byweight, or at least 99% by weight, of the firm-forming polymer is notdissolved in the aqueous medium.

Any suitable firm-forming polymer can be used. Film-forming polymersthat are dispersible in the aqueous medium are generally preferred. Insome embodiments, the film-forming polymer is a natural latex. In someother embodiments, the film-forming polymer is a synthetic latex. Suchsynthetic latexes include, but are not limited to, acrylic polymers,polyvinyl acetate, polyvinyl chloride, styrene-butadiene rubber, otherstyrene polymers, acrylonitrile-butadiene rubber, epoxy resins, or anymixture thereof. In some embodiments, the firm-forming polymer is amixture of a natural latex and one or more synthetic latex compositions.Certain polymers suitable for use in paint and coating applications areavailable commercially. A non-limiting example is RHOPLEX SG-30 acrylicresin (Dow Chemical Co., Midland, Mich., USA).

Any suitable amount of film-forming polymer can be used. The amount canvary depending on a variety of factors, including, but not limited to,the desired thickness of the composition, the desired end use of thecomposition, the properties of the film-forming polymer, the identity ofother components in the composition, and the like. In some embodiments,the weight-to-weight ratio of film-forming polymer to water in thecomposition ranges from 1:2 to 10:1, or from 1:1 to 8:1, or from 2:1 to6:1, or from 3:1 to 5:1. In embodiments where a co-solvent is used inaddition to water, the foregoing ratios would apply to the total weightof solvent (water plus any co-solvents) and not exclusively to thewater.

The compositions disclosed herein also include a coalescing aid, whichincludes one or more polyol esters of unsaturated fatty acids (accordingto any of the above embodiments).

As discussed in further detail below, in some embodiments, the one ormore unsaturated fatty acids used to make the polyol esters thereof canbe derived from a renewable source, such as from a natural oil. In somesuch embodiments, the one or more polyol esters of unsaturated fattyacids are derived from a process that includes metathesizing a naturaloil or a natural oil derivative. Further details regarding suchprocesses are provided below.

In some embodiments, the coalescing aid predominantly contains one ormore polyol esters of unsaturated fatty acids according to any of theabove embodiments. For example, in some embodiments, the one or morepolyol esters of unsaturated fatty acids make up at least 50% by weight,or at least 60% by weight, or at least 70% by weight, or at least 80% byweight, or at least 90% by weight, or at least 95% by weight, or atleast 97% by weight, or at least 99% by weight, of the coalescing aid.In some embodiments, the coalescing aid contains alkyl esters (e.g.,methyl esters) of unsaturated C₁₂₋₁₆ carboxylic acids, including, butnot limited to, 9-dodecenoic acid, 9,12-tridecadienoic acid,11-tetradecanoic acid, 9-pentadecanoic acid, 9,12-pentadecadienoic acid.In some embodiments, the alkyl esters (e.g., methyl esters) ofunsaturated C₁₂₋₁₆ carboxylic acids make up at least 50% by weight, orat least 60% by weight, or at least 70% by weight, or at least 80% byweight, or at least 90% by weight, or at least 95% by weight, or atleast 97% by weight, or at least 99% by weight, of the coalescing aid.

The coalescing aid can also include some amount of esters (e.g., alkylesters, such as methyl esters) of saturated carboxylic acids.Non-limiting examples include myristic acid, palmitic acid, and stearicacid. In embodiments where such saturated esters are present, they makeup no more than 50% by weight, or no more than 40% by weight, or no morethan 30% by weight, or no more than 20% by weight, or no more than 10%by weight.

In some embodiments, the coalescing aid can include one or more othercompounds that can aid in the coalescing of the film-forming polymers.Suitable additional ingredients in the coalescing aid include, but arenot limited to, 2,2,4-trimethyl-1,3-pentanediol isobutyrate,commercially available as TEXANOL (Eastman Chem. Co., Kingsport, Tenn.,USA).

Any suitable amount of the coalescing aid can be used in thecomposition. The amount can vary depending on a variety of factors,including, but not limited to, the desired end use of the composition,the properties of the film-forming polymer, the identity of thecomponents in the coalescing aid, and the like. In some embodiments, theweight-to-weight ratio of film-forming polymer to coalescing aid rangesfrom 5:1 to 200:1, or from 10:1 to 100:1, or from 15:1 to 60:1. In someembodiments, the weight-to-weight ratio of water to coalescing aidranges from 4:1 to 100:1, or from 6:1 to 50:1, or from 8:1 to 25:1, orfrom 10:1 to 20:1. In embodiments where a co-solvent is used in additionto water, the foregoing ratios would apply to the total weight ofsolvent (water plus any co-solvents) and not exclusively to the water.

The composition can contain various other ingredients. In someembodiments, the composition can contain one or more colorants, such aspigments, dyes, and the like. Such colorants can be organic orinorganic, synthetic or natural. Non-limiting examples of suitablepigments include cadmium yellow, cadmium red, cadmium green, cadmiumorange, carbon black (including vine black, lamp black), ivory black(bone char), chrome yellow, chrome green, cobalt violet, cobalt blue,cerulean blue, aureolin (cobalt yellow), Azurite, Han purple, Han blue,Egyptian blue, Malachite, Paris green, Phthalocyanine Blue BN,Phthalocyanine Green G, verdigris, viridian, sanguine, caput mortuum,oxide red, red ochre, Venetian red, Prussian blue, yellow ochre, rawsienna, burnt sienna, raw umber, burnt umber, lead white, cremnitzwhite, Naples yellow, red lead, vermilion titanium yellow, titaniumbeige, titanium white (TiO₂), titanium black, ultramarine, ultramarinegreen shade, zinc white, zinc ferrite, alizarin (synthesized ornatural), alizarin crimson (synthesized or natural), gamboge, cochinealred, rose madder, indigo, Indian yellow, Tyrian purple, quinacridone,magenta, phthalo green, phthalo blue, pigment red 170, or anycombinations thereof. In some embodiments, the composition at leastincludes titanium white (TiO₂).

Other ingredients can also be present in the composition. For example,in some embodiments, the composition includes one or more thickeners,one or more rheology modifiers, one or more surfactants, one or moredefoamers, or any combination thereof. In some embodiments, thecomposition can include one or more biocide compounds.

Further, in some embodiments, the composition is an environmentallyfriendly composition, for example, that contains a low content ofvolatile organic components (VOCs). In some embodiments, the compositionincludes no more than 0.5 kg/L, or no more than 0.3 kg/L, or no morethan 0.1 kg/L, of VOCs, as measured by Method 24 of the United StatesEnvironmental Protection Agency.

The above compositions can be put to a wide variety of different uses.For example, in some non-limiting examples, the compositions aresuitable for use as paint or coating compositions. In some embodiments,the composition is an interior paint composition. In some otherembodiments, the composition is an exterior paint composition.

Derivation from Renewable Sources

The polyol esters of unsaturated fatty acids employed in any of theaspects and embodiments disclosed herein can, in certain embodiments, bederived from renewable sources, such as various natural oils. Anysuitable methods can be used to make these compounds from such renewablesources. Suitable methods include, but are not limited to, fermentation,conversion by bioorganisms, and conversion by metathesis.

Olefin metathesis provides one possible means to convert certain naturaloil feedstocks into olefins and esters that can be used in a variety ofapplications, or that can be further modified chemically and used in avariety of applications. In some embodiments, a composition (orcomponents of a composition) may be formed from a renewable feedstock,such as a renewable feedstock formed through metathesis reactions ofnatural oils and/or their fatty acid or fatty ester derivatives. Whencompounds containing a carbon-carbon double bond undergo metathesisreactions in the presence of a metathesis catalyst, some or all of theoriginal carbon-carbon double bonds are broken, and new carbon-carbondouble bonds are formed. The products of such metathesis reactionsinclude carbon-carbon double bonds in different locations, which canprovide unsaturated organic compounds having useful chemical properties.

A wide range of natural oils, or derivatives thereof, can be used insuch metathesis reactions. Examples of suitable natural oils include,but are not limited to, vegetable oils, algae oils, fish oils, animalfats, tall oils, derivatives of these oils, combinations of any of theseoils, and the like. Representative non-limiting examples of vegetableoils include rapeseed oil (canola oil), coconut oil, corn oil,cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesameoil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil,jatropha oil, mustard seed oil, pennycress oil, camelina oil, hempseedoil, and castor oil. Representative non-limiting examples of animal fatsinclude lard, tallow, poultry fat, yellow grease, and fish oil. Talloils are by-products of wood pulp manufacture. In some embodiments, thenatural oil or natural oil feedstock comprises one or more unsaturatedglycerides (e.g., unsaturated triglycerides). In some such embodiments,the natural oil feedstock comprises at least 50% by weight, or at least60% by weight, or at least 70% by weight, or at least 80% by weight, orat least 90% by weight, or at least 95% by weight, or at least 97% byweight, or at least 99% by weight of one or more unsaturatedtriglycerides, based on the total weight of the natural oil feedstock.

The natural oil may include canola or soybean oil, such as refined,bleached and deodorized soybean oil (i.e., RBD soybean oil). Soybean oiltypically includes about 95 percent by weight (wt %) or greater (e.g.,99 wt % or greater) triglycerides of fatty acids. Major fatty acids inthe polyol esters of soybean oil include but are not limited tosaturated fatty acids such as palmitic acid (hexadecanoic acid) andstearic acid (octadecanoic acid), and unsaturated fatty acids such asoleic acid (9-octadecenoic acid), linoleic acid (9,12-octadecadienoicacid), and linolenic acid (9,12,15-octadecatrienoic acid).

Metathesized natural oils can also be used. Examples of metathesizednatural oils include but are not limited to a metathesized vegetableoil, a metathesized algal oil, a metathesized animal fat, a metathesizedtall oil, a metathesized derivatives of these oils, or mixtures thereof.For example, a metathesized vegetable oil may include metathesizedcanola oil, metathesized rapeseed oil, metathesized coconut oil,metathesized corn oil, metathesized cottonseed oil, metathesized oliveoil, metathesized palm oil, metathesized peanut oil, metathesizedsafflower oil, metathesized sesame oil, metathesized soybean oil,metathesized sunflower oil, metathesized linseed oil, metathesized palmkernel oil, metathesized tung oil, metathesized jatropha oil,metathesized mustard oil, metathesized camelina oil, metathesizedpennycress oil, metathesized castor oil, metathesized derivatives ofthese oils, or mixtures thereof. In another example, the metathesizednatural oil may include a metathesized animal fat, such as metathesizedlard, metathesized tallow, metathesized poultry fat, metathesized fishoil, metathesized derivatives of these oils, or mixtures thereof.

Such natural oils, or derivatives thereof, can contain esters, such astriglycerides, of various unsaturated fatty acids. The identity andconcentration of such fatty acids varies depending on the oil source,and, in some cases, on the variety. In some embodiments, the natural oilcomprises one or more esters of oleic acid, linoleic acid, linolenicacid, or any combination thereof. When such fatty acid esters aremetathesized, new compounds are formed. For example, in embodimentswhere the metathesis uses certain short-chain olefins, e.g., ethylene,propylene, or 1-butene, and where the natural oil includes esters ofoleic acid, an amount of 1-decene and 1-decenoid acid (or an esterthereof), among other products, are formed. Followingtransesterification, for example, with an alkyl alcohol, an amount of9-denenoic acid alkyl ester is formed. In some such embodiments, aseparation step may occur between the metathesis and thetransesterification, where the alkenes are separated from the esters. Insome other embodiments, transesterification can occur before metathesis,and the metathesis is performed on the transesterified product.

In some embodiments, the natural oil can be subjected to variouspre-treatment processes, which can facilitate their utility for use incertain metathesis reactions. Useful pre-treatment methods are describedin United States Patent Application Publication Nos. 2011/0113679,2014/0275595, and 2014/0275681, all three of which are herebyincorporated by reference as though fully set forth herein.

In some embodiments, after any optional pre-treatment of the natural oilfeedstock, the natural oil feedstock is reacted in the presence of ametathesis catalyst in a metathesis reactor. In some other embodiments,an unsaturated ester (e.g., an unsaturated glyceride, such as anunsaturated triglyceride) is reacted in the presence of a metathesiscatalyst in a metathesis reactor. These polyol esters of unsaturatedfatty acids may be a component of a natural oil feedstock, or may bederived from other sources, e.g., from esters generated inearlier-performed metathesis reactions. In certain embodiments, in thepresence of a metathesis catalyst, the natural oil or unsaturated estercan undergo a self-metathesis reaction with itself. In otherembodiments, the natural oil or unsaturated ester undergoes across-metathesis reaction with the low-molecular-weight olefin ormid-weight olefin. The self-metathesis and/or cross-metathesis reactionsform a metathesized product wherein the metathesized product comprisesolefins and esters.

In some embodiments, the low-molecular-weight olefin is in the C₂₋₆range. As a non-limiting example, in one embodiment, thelow-molecular-weight olefin may comprise at least one of: ethylene,propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene,3-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene,cyclopentene, 1,4-pentadiene, 1-hexene, 2-hexene, 3-hexene, 4-hexene,2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-2-pentene,2-methyl-3-pentene, and cyclohexene. In some instances, ahigher-molecular-weight olefin can also be used.

In some embodiments, the metathesis comprises reacting a natural oilfeedstock (or another unsaturated ester) in the presence of a metathesiscatalyst. In some such embodiments, the metathesis comprises reactingone or more unsaturated glycerides (e.g., unsaturated triglycerides) inthe natural oil feedstock in the presence of a metathesis catalyst. Insome embodiments, the unsaturated glyceride comprises one or more estersof oleic acid, linoleic acid, linoleic acid, or combinations thereof. Insome other embodiments, the unsaturated glyceride is the product of thepartial hydrogenation and/or the metathesis of another unsaturatedglyceride (as described above). In some such embodiments, the metathesisis a cross-metathesis of any of the aforementioned unsaturatedtriglyceride species with another olefin, e.g., an alkene. In some suchembodiments, the alkene used in the cross-metathesis is a lower alkene,such as ethylene, propylene, 1-butene, 2-butene, etc. In someembodiments, the alkene is ethylene. In some other embodiments, thealkene is propylene. In some further embodiments, the alkene is1-butene. And in some even further embodiments, the alkene is 2-butene.

Metathesis reactions can provide a variety of useful products, whenemployed in the methods disclosed herein. For example, the polyol estersof unsaturated fatty acids may be derived from a natural oil feedstock,in addition to other valuable compositions. Moreover, in someembodiments, a number of valuable compositions can be targeted throughthe self-metathesis reaction of a natural oil feedstock, or thecross-metathesis reaction of the natural oil feedstock with alow-molecular-weight olefin or mid-weight olefin, in the presence of ametathesis catalyst. Such valuable compositions can include fuelcompositions, detergents, surfactants, and other specialty chemicals.Additionally, transesterified products (i.e., the products formed fromtransesterifying an ester in the presence of an alcohol) may also betargeted, non-limiting examples of which include: fatty acid methylesters (“FAMEs”); biodiesel; 9-decenoic acid (“9DA”) esters,9-undecenoic acid (“9UDA”) esters, and/or 9-dodecenoic acid (“9DDA”)esters; 9DA, 9UDA, and/or 9DDA; alkali metal salts and alkaline earthmetal salts of 9DA, 9UDA, and/or 9DDA; dimers of the transesterifiedproducts; and mixtures thereof.

Further, in some embodiments, multiple metathesis reactions can also beemployed. In some embodiments, the multiple metathesis reactions occursequentially in the same reactor. For example, a glyceride containinglinoleic acid can be metathesized with a terminal lower alkene (e.g.,ethylene, propylene, 1-butene, and the like) to form 1,4-decadiene,which can be metathesized a second time with a terminal lower alkene toform 1,4-pentadiene. In other embodiments, however, the multiplemetathesis reactions are not sequential, such that at least one otherstep (e.g., transesterification, hydrogenation, etc.) can be performedbetween the first metathesis step and the following metathesis step.These multiple metathesis procedures can be used to obtain products thatmay not be readily obtainable from a single metathesis reaction usingavailable starting materials. For example, in some embodiments, multiplemetathesis can involve self-metathesis followed by cross-metathesis toobtain metathesis dimers, trimmers, and the like. In some otherembodiments, multiple metathesis can be used to obtain olefin and/orester components that have chain lengths that may not be achievable froma single metathesis reaction with a natural oil triglyceride and typicallower alkenes (e.g., ethylene, propylene, 1-butene, 2-butene, and thelike). Such multiple metathesis can be useful in an industrial-scalereactor, where it may be easier to perform multiple metathesis than tomodify the reactor to use a different alkene.

The conditions for such metathesis reactions, and the reactor design,and suitable catalysts are as described above with reference to themetathesis of the olefin esters. That discussion is incorporated byreference as though fully set forth herein.

In the embodiments above, the natural oil (e.g., as a glyceride) ismetathesized, followed by transesterification. In some otherembodiments, transesterification can precede metathesis, such that thefatty acid esters subjected to metathesis are fatty acid esters ofmonohydric alcohols, such as methanol, ethanol, or isopropanol.

Olefin Metathesis

In some embodiments, one or more of the unsaturated monomers can be madeby metathesizing a natural oil or natural oil derivative. The terms“metathesis” or “metathesizing” can refer to a variety of differentreactions, including, but not limited to, cross-metathesis,self-metathesis, ring-opening metathesis, ring-opening metathesispolymerizations (“ROMP”), ring-closing metathesis (“RCM”), and acyclicdiene metathesis (“ADMET”). Any suitable metathesis reaction can beused, depending on the desired product or product mixture.

In some embodiments, after any optional pre-treatment of the natural oilfeedstock, the natural oil feedstock is reacted in the presence of ametathesis catalyst in a metathesis reactor. In some other embodiments,an unsaturated ester (e.g., an unsaturated glyceride, such as anunsaturated triglyceride) is reacted in the presence of a metathesiscatalyst in a metathesis reactor. These unsaturated esters may be acomponent of a natural oil feedstock, or may be derived from othersources, e.g., from esters generated in earlier-performed metathesisreactions. In certain embodiments, in the presence of a metathesiscatalyst, the natural oil or unsaturated ester can undergo aself-metathesis reaction with itself. In other embodiments, the naturaloil or unsaturated ester undergoes a cross-metathesis reaction with thelow-molecular-weight olefin or mid-weight olefin. The self-metathesisand/or cross-metathesis reactions form a metathesized product whereinthe metathesized product comprises olefins and esters.

In some embodiments, the low-molecular-weight olefin is in the C₂₋₆range. As a non-limiting example, in one embodiment, thelow-molecular-weight olefin may comprise at least one of: ethylene,propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene,3-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene,cyclopentene, 1,4-pentadiene, 1-hexene, 2-hexene, 3-hexene, 4-hexene,2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-2-pentene,2-methyl-3-pentene, and cyclohexene. In some instances, ahigher-molecular-weight olefin can also be used.

In some embodiments, the metathesis comprises reacting a natural oilfeedstock (or another unsaturated ester) in the presence of a metathesiscatalyst. In some such embodiments, the metathesis comprises reactingone or more unsaturated glycerides (e.g., unsaturated triglycerides) inthe natural oil feedstock in the presence of a metathesis catalyst. Insome embodiments, the unsaturated glyceride comprises one or more estersof oleic acid, linoleic acid, linoleic acid, or combinations thereof. Insome other embodiments, the unsaturated glyceride is the product of thepartial hydrogenation and/or the metathesis of another unsaturatedglyceride (as described above). In some such embodiments, the metathesisis a cross-metathesis of any of the aforementioned unsaturatedtriglyceride species with another olefin, e.g., an alkene. In some suchembodiments, the alkene used in the cross-metathesis is a lower alkene,such as ethylene, propylene, 1-butene, 2-butene, etc. In someembodiments, the alkene is ethylene. In some other embodiments, thealkene is propylene. In some further embodiments, the alkene is1-butene. And in some even further embodiments, the alkene is 2-butene.

Metathesis reactions can provide a variety of useful products, whenemployed in the methods disclosed herein. For example, terminal olefinsand internal olefins may be derived from a natural oil feedstock, inaddition to other valuable compositions. Moreover, in some embodiments,a number of valuable compositions can be targeted through theself-metathesis reaction of a natural oil feedstock, or thecross-metathesis reaction of the natural oil feedstock with alow-molecular-weight olefin or mid-weight olefin, in the presence of ametathesis catalyst. Such valuable compositions can include fuelcompositions, detergents, surfactants, and other specialty chemicals.Additionally, transesterified products (i.e., the products formed fromtransesterifying an ester in the presence of an alcohol) may also betargeted, non-limiting examples of which include: fatty acid methylesters (“FAMEs”); biodiesel; 9-decenoic acid (“9DA”) esters,9-undecenoic acid (“9UDA”) esters, and/or 9-dodecenoic acid (“9DDA”)esters; 9DA, 9UDA, and/or 9DDA; alkali metal salts and alkaline earthmetal salts of 9DA, 9UDA, and/or 9DDA; dimers of the transesterifiedproducts; and mixtures thereof.

Further, in some embodiments, the methods disclosed herein can employmultiple metathesis reactions. In some embodiments, the multiplemetathesis reactions occur sequentially in the same reactor. Forexample, a glyceride containing linoleic acid can be metathesized with aterminal lower alkene (e.g., ethylene, propylene, 1-butene, and thelike) to form 1,4-decadiene, which can be metathesized a second timewith a terminal lower alkene to form 1,4-pentadiene. In otherembodiments, however, the multiple metathesis reactions are notsequential, such that at least one other step (e.g.,transesterification, hydrogenation, etc.) can be performed between thefirst metathesis step and the following metathesis step. These multiplemetathesis procedures can be used to obtain products that may not bereadily obtainable from a single metathesis reaction using availablestarting materials. For example, in some embodiments, multiplemetathesis can involve self-metathesis followed by cross-metathesis toobtain metathesis dimers, trimmers, and the like. In some otherembodiments, multiple metathesis can be used to obtain olefin and/orester components that have chain lengths that may not be achievable froma single metathesis reaction with a natural oil triglyceride and typicallower alkenes (e.g., ethylene, propylene, 1-butene, 2-butene, and thelike). Such multiple metathesis can be useful in an industrial-scalereactor, where it may be easier to perform multiple metathesis than tomodify the reactor to use a different alkene.

The metathesis process can be conducted under any conditions adequate toproduce the desired metathesis products. For example, stoichiometry,atmosphere, solvent, temperature, and pressure can be selected by oneskilled in the art to produce a desired product and to minimizeundesirable byproducts. In some embodiments, the metathesis process maybe conducted under an inert atmosphere. Similarly, in embodiments were areagent is supplied as a gas, an inert gaseous diluent can be used inthe gas stream. In such embodiments, the inert atmosphere or inertgaseous diluent typically is an inert gas, meaning that the gas does notinteract with the metathesis catalyst to impede catalysis to asubstantial degree. For example, non-limiting examples of inert gasesinclude helium, neon, argon, and nitrogen, used individually or in witheach other and other inert gases.

The rector design for the metathesis reaction can vary depending on avariety of factors, including, but not limited to, the scale of thereaction, the reaction conditions (heat, pressure, etc.), the identityof the catalyst, the identity of the materials being reacted in thereactor, and the nature of the feedstock being employed. Suitablereactors can be designed by those of skill in the art, depending on therelevant factors, and incorporated into a refining process such, such asthose disclosed herein.

The metathesis reactions disclosed herein generally occur in thepresence of one or more metathesis catalysts. Such methods can employany suitable metathesis catalyst. The metathesis catalyst in thisreaction may include any catalyst or catalyst system that catalyzes ametathesis reaction. Any known metathesis catalyst may be used, alone orin combination with one or more additional catalysts. Examples ofmetathesis catalysts and process conditions are described in US2011/0160472, incorporated by reference herein in its entirety, exceptthat in the event of any inconsistent disclosure or definition from thepresent specification, the disclosure or definition herein shall bedeemed to prevail. A number of the metathesis catalysts described in US2011/0160472 are presently available from Materia, Inc. (Pasadena,Calif.).

In some embodiments, the metathesis catalyst includes a Grubbs-typeolefin metathesis catalyst and/or an entity derived therefrom. In someembodiments, the metathesis catalyst includes a first-generationGrubbs-type olefin metathesis catalyst and/or an entity derivedtherefrom. In some embodiments, the metathesis catalyst includes asecond-generation Grubbs-type olefin metathesis catalyst and/or anentity derived therefrom. In some embodiments, the metathesis catalystincludes a first-generation Hoveyda-Grubbs-type olefin metathesiscatalyst and/or an entity derived therefrom. In some embodiments, themetathesis catalyst includes a second-generation Hoveyda-Grubbs-typeolefin metathesis catalyst and/or an entity derived therefrom. In someembodiments, the metathesis catalyst includes one or a plurality of theruthenium carbene metathesis catalysts sold by Materia, Inc. ofPasadena, Calif. and/or one or more entities derived from suchcatalysts. Representative metathesis catalysts from Materia, Inc. foruse in accordance with the present teachings include but are not limitedto those sold under the following product numbers as well ascombinations thereof: product no. C823 (CAS no. 172222-30-9), productno. C848 (CAS no. 246047-72-3), product no. C601 (CAS no. 203714-71-0),product no. C627 (CAS no. 301224-40-8), product no. C571 (CAS no.927429-61-6), product no. C598 (CAS no. 802912-44-3), product no. C793(CAS no. 927429-60-5), product no. C801 (CAS no. 194659-03-9), productno. C827 (CAS no. 253688-91-4), product no. C884 (CAS no. 900169-53-1),product no. C833 (CAS no. 1020085-61-3), product no. C859 (CAS no.832146-68-6), product no. C711 (CAS no. 635679-24-2), product no. C933(CAS no. 373640-75-6).

In some embodiments, the metathesis catalyst includes a molybdenumand/or tungsten carbene complex and/or an entity derived from such acomplex. In some embodiments, the metathesis catalyst includes aSchrock-type olefin metathesis catalyst and/or an entity derivedtherefrom. In some embodiments, the metathesis catalyst includes ahigh-oxidation-state alkylidene complex of molybdenum and/or an entityderived therefrom. In some embodiments, the metathesis catalyst includesa high-oxidation-state alkylidene complex of tungsten and/or an entityderived therefrom. In some embodiments, the metathesis catalyst includesmolybdenum (VI). In some embodiments, the metathesis catalyst includestungsten (VI). In some embodiments, the metathesis catalyst includes amolybdenum- and/or a tungsten-containing alkylidene complex of a typedescribed in one or more of (a) Angew. Chem. Int. Ed. Engl., 2003, 42,4592-4633; (b) Chem. Rev., 2002, 102, 145-179; and/or (c) Chem. Rev.,2009, 109, 3211-3226, each of which is incorporated by reference hereinin its entirety, except that in the event of any inconsistent disclosureor definition from the present specification, the disclosure ordefinition herein shall be deemed to prevail.

In certain embodiments, the metathesis catalyst is dissolved in asolvent prior to conducting the metathesis reaction. In certain suchembodiments, the solvent chosen may be selected to be substantiallyinert with respect to the metathesis catalyst. For example,substantially inert solvents include, without limitation: aromatichydrocarbons, such as benzene, toluene, xylenes, etc.; halogenatedaromatic hydrocarbons, such as chlorobenzene and dichlorobenzene;aliphatic solvents, including pentane, hexane, heptane, cyclohexane,etc.; and chlorinated alkanes, such as dichloromethane, chloroform,dichloroethane, etc. In some embodiments, the solvent comprises toluene.

In other embodiments, the metathesis catalyst is not dissolved in asolvent prior to conducting the metathesis reaction. The catalyst,instead, for example, can be slurried with the natural oil orunsaturated ester, where the natural oil or unsaturated ester is in aliquid state. Under these conditions, it is possible to eliminate thesolvent (e.g., toluene) from the process and eliminate downstream olefinlosses when separating the solvent. In other embodiments, the metathesiscatalyst may be added in solid state form (and not slurried) to thenatural oil or unsaturated ester (e.g., as an auger feed).

The metathesis reaction temperature may, in some instances, be arate-controlling variable where the temperature is selected to provide adesired product at an acceptable rate. In certain embodiments, themetathesis reaction temperature is greater than −40° C., or greater than−20° C., or greater than 0° C., or greater than 10° C. In certainembodiments, the metathesis reaction temperature is less than 200° C.,or less than 150° C., or less than 120° C. In some embodiments, themetathesis reaction temperature is between 0° C. and 150° C., or isbetween 10° C. and 120° C.

The metathesis reaction can be run under any desired pressure. In someinstances, it may be desirable to maintain a total pressure that is highenough to keep the cross-metathesis reagent in solution. Therefore, asthe molecular weight of the cross-metathesis reagent increases, thelower pressure range typically decreases since the boiling point of thecross-metathesis reagent increases. The total pressure may be selectedto be greater than 0.1 atm (10 kPa), or greater than 0.3 atm (30 kPa),or greater than 1 atm (100 kPa). In some embodiments, the reactionpressure is no more than about 70 atm (7000 kPa), or no more than about30 atm (3000 kPa). In some embodiments, the pressure for the metathesisreaction ranges from about 1 atm (100 kPa) to about 30 atm (3000 kPa).

Methods of Making Compositions

In certain aspects, the disclosure provides processes for makingcompositions according to any of the above embodiments.

The compositions disclosed herein can be made by any suitable process.In embodiments where the composition is a paint or coating composition,typical methods of making paint or coating compositions can be employed.For example, in some embodiments, certain materials (e.g., insolublematerials) can be ground together in a paste. The paste can then bedispersed into the aqueous medium with the polymer droplets suspendedtherein (e.g., as an emulsion).

Methods of Reducing the Minimum Film-Forming Temperature of a Polymer

In certain aspects, the disclosure provides methods of reducing theminimum film-forming temperature of a polymer.

In some embodiments, the method includes: providing a polymercomposition, which comprises a film-forming polymer; and contacting thefirm-forming polymer with a coalescing aid, which comprises one or morecompounds unsaturated ester compounds according to any of the aboveembodiments. In some such embodiments, the method includes incorporatingthe film-forming polymer and the coalescing aid into a compositionaccording to any of the above embodiments.

Methods of Painting or Coating a Surface

In certain aspects, the disclosure provides methods of painting orcoating a surface. In some embodiments, the surface is an interiorsurface, such as an interior wall, an interior ceiling, interiorwoodwork, and the like.

In some embodiments, the method includes: providing a surface; andcontacting the surface with a composition according to any of the aboveembodiments. In some such embodiments, the method includes painting thecomposition onto the surface, for example, with a suitable applicator,such as a brush, roller, sprayer, and the like.

EXAMPLES Example 1 2-Hydroxypropyl 9-dodecenoate

1,2-Propylene glycol (99%) (208 g, 2.73 mol) was sparged with nitrogenfor 30 min and heated to 135 C. Sodium methoxide (25% w/w in MeOH) (17.6mL, 0.077 mol) was added and the solution stirred for 20 min. Next,methyl-9-dodecenoate (430 g, 2.03 mol) was added dropwise over 3 h andthe reaction stirred for an additional 1.5 h with continuous removal ofmethanol into a dry ice cooled trap. A second charge of propylene glycol(99%) (114 g, 1.50 mol) was added and the reaction continued at 135 Cfor 1 h. The reaction was cooled to room temperature and the catalystquenched to neutrality with phosphoric acid (85%) resulting in a sodiumphosphate precipitate. The desired monoester product was purified byvacuum distillation to yield an odorless, colorless oil (445 g, 1.74mol, 86%). GC-MS m/z calcd for C₁₅H₂₈O₃(M)⁺: 256.2, found: 256.1. ¹H NMR(400 MHz, CDCl₃): δ=0.96 (t, 3H), 1.20-1.30 (bm, 13H), 1.62 (m, 2H),1.97 (m, 4H), 2.35 (m, 2H), 2.55 (bs, 1H), 3.91-4.12 (m, 2H), 5.32-5.46(m, 2H). Density=0.894 g/mL. Percent volatile content (ASTM D2369)=32.9g/L.

The 2-hydroxypropyl 9-dodecenoate was tested as a coalescent in astandard latex paint formulation, and, upon drying, yielded a painthaving suitable film-forming and other performance-related properties.

Example 2 3-Hydroxypropyl 9-dodecenoate

3-Hydroxypropyl 9-dodecenoate was made in a manner analogous to themethod of Example 1, but using 1,3-propylene glycol instead of1,2-propylene glycol. ¹H NMR (CDCl₃): δ=0.88 (t, 3H, J=7.2 Hz), 1.23(bm, 8H), 1.56 (m, 2H); 1.79 (m, 2H), 1.92 (m, 4H), 2.24 (t, 2H, J=7.6Hz), 2.53 (bs, 1H), 3.61 (t, 2H, J=6.0 Hz), 4.15 (t, 2H, J=6.0 Hz), 5.30(m, 2H).

The 3-hydroxypropyl 9-dodecenoate was tested as a coalescent in astandard latex paint formulation, and, upon drying, yielded a painthaving suitable film-forming and other performance-related properties.

Example 3 3-Hydroxy-2-methylpropyl 9-dodecenoate

3-Hydroxy-2-methylpropyl 9-dodecenoate was made in a manner analogous tothe method of Example 1, but using 2-methyl-1,3-propane diol instead of1,2-propylene glycol.

The 3-hydroxy-2-methylpropyl 9-dodecenoate was tested as a coalescent ina standard latex paint formulation, and, upon drying, yielded a painthaving suitable film-forming and other performance-related properties.

Example 4 4-Hydroxybutyl 9-dodecenoate

4-Hydroxybutyl 9-dodecenoate was made in a manner analogous to themethod of Example 1, but using 1,4-butane diol instead of 1,2-propyleneglycol.

The 4-hydroxybutyl 9-dodecenoate was tested as a coalescent in astandard latex paint formulation, and, upon drying, yielded a painthaving suitable film-forming and other performance-related properties.

Example 5 3-Hydroxy-2,2,4-trimethylpentyl 9-dodecenoate

3-Hydroxy-2,2,4-trimethylpentyl 9-dodecenoate is made in a manneranalogous to the method of Example 1, but using2,2,4-trimethyl-1,3-pentane diol instead of 1,2-propylene glycol.

The 3-hydroxy-2,2,4-trimethylpentyl 9-dodecenoate is tested as acoalescent in a standard latex paint formulation, and, upon drying,yields a paint having suitable film-forming and otherperformance-related properties.

What is claimed is:
 1. A paint or coating composition, comprising: afilm-forming polymer; water; and a compound of formula (I):

wherein: R¹ is —H, —CH₂—CH₃, —CH₂—CH═CH₂, or —CH₂—CH═CH—CH₂—CH₃; R² is—(C₂₋₁₀ alkylene)-(OH)q; and q is 1 or
 2. 2. The composition of claim 1,wherein the film-forming polymer is a natural latex, a synthetic latex,or a mixture thereof.
 3. The composition of claim 2, where thefilm-forming polymer is a synthetic latex.
 4. The composition of claim3, where the synthetic latex is an acrylic polymer, polyvinyl acetate,polyvinyl chloride, styrene-butadiene rubber, acrylonitrile-butadienerubber, or a mixture thereof.
 5. The composition of claim 1, wherein theweight-to-weight ratio of film-forming polymer to compound ranges from5:1 to 200:1.
 6. The composition of claim 1, wherein the composition hasno more than 0.5 kg/L of volatile organic compounds (VOCs), as measuredby Method 24 of the United States Environmental Protection Agency. 7.The composition of claim 1, wherein R¹ is —H.
 8. The compound of claim1, wherein R¹ is —CH₂—CH₃.
 9. The compound of claim 1, wherein R² is—(C₂₋₁₀ alkylene)-OH.
 10. The compound of claim 9, wherein R² is—(CH₂)₂—OH, —(CH₂)₃—OH, —(CH₂)₄—OH, —(CH₂)₅—OH, —(CH₂)₆—OH, —CH(OH)—CH₃,—CH₂—CH(OH)—CH₃, —CH(CH₃)—CH₂—OH, —CH₂—CH(CH₃)—CH₂—OH, or—CH₂—C(CH₃)₂—CH(OH)—CH(CH₃)₂.
 11. The compound of claim 10, wherein R²is —(CH₂)₂—OH.
 12. The compound of claim 10, wherein R² is —(CH₂)₃—OH.13. The compound of claim 10, wherein R² is —(CH₂)₄—OH.
 14. The compoundof claim 10, wherein R² is —CH(OH)—CH₃.
 15. The compound of claim 10,wherein R² is —CH₂—CH(OH)—CH₃.
 16. The compound of claim 10, wherein R²is —CH(CH₃)—CH₂—OH.
 17. The compound of claim 10, wherein R² is—CH₂—CH(CH₃)—CH₂—OH.
 18. The compound of claim 10, wherein R² is—CH₂—C(CH₃)₂—CH(OH)—CH(CH₃)₂.